CN109088119B - Method for recycling lithium in waste graphite system lithium ion battery negative electrode plate - Google Patents
Method for recycling lithium in waste graphite system lithium ion battery negative electrode plate Download PDFInfo
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- CN109088119B CN109088119B CN201810942393.6A CN201810942393A CN109088119B CN 109088119 B CN109088119 B CN 109088119B CN 201810942393 A CN201810942393 A CN 201810942393A CN 109088119 B CN109088119 B CN 109088119B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/04—Halides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/06—Sulfates; Sulfites
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
A method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery comprises the following steps: step one, fully charging the waste graphite lithium ion battery; step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell; step three, the negative pole piece obtained in the step two is placed at the temperature of 150-550 ℃ for heat treatment; step four, adding water into the negative plate subjected to heat treatment in the step three according to the solid-liquid ratio of 1:10-1:3, and stirring for 0.5-4h to obtain a solid-liquid mixture; step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 20-80 meshes to obtain metal copper and an aqueous solution containing graphite powder; and step six, adding sulfuric acid or hydrochloric acid into the aqueous solution containing the graphite powder obtained in the step five to adjust the pH value of the solution to 0.5-2.0, and then filtering to obtain the solution containing the graphite powder and the lithium compound. The method can separate more than 17g of lithium from the negative pole piece of the 1kg waste graphite lithium ion battery, and has extremely wide application prospect.
Description
Technical Field
The invention relates to the field of lithium recovery, in particular to a method for recovering lithium in a negative plate of a waste graphite lithium ion battery.
Background
The graphite lithium battery normally works by utilizing the reverse movement of lithium ions and electrons stored in a positive electrode material in the charging and discharging process, wherein the positive electrode material generally adopts lithium alloy metal oxides, such as lithium cobaltate, lithium manganate, lithium manganese phosphate and the like, and the negative electrode material adopts graphite. The graphite lithium ion battery is easy to generate the phenomenon that lithium is deposited on a negative plate without being removed in time in the using process, and particularly the waste lithium ion battery with less than half of capacity left after echelon utilization. In addition, after abuse under high and low temperature, overcharge and overdischarge or other special working conditions, the deposition of lithium on the negative plate is also serious. Through disassembly, the surface of the negative plate is provided with a large amount of yellow metallic lithium simple substance, and the yellow metallic lithium simple substance is rapidly oxidized in the air. If the lithium deposited on the negative electrode plate cannot be recovered by adopting a reasonable method, not only is the waste of lithium resources caused, but also the environmental pollution is caused.
Chinese patent publication No. CN107394298A discloses a method for recovering lithium resources on a negative electrode plate of a waste lithium ion battery, which comprises the following steps: firstly, preparing the blocky powder on the surface of the negative plate into fine powder, and assisting ultrasonic stirring in the reaction process of the blocky powder and dilute hydrochloric acid, thereby realizing the leaching of lithium resources. Although this method can obtain lithium carbonate powder with high purity, the leaching rate is not high, and the recovery rate of lithium is low.
In summary, no method for recovering lithium from the negative electrode plate of the waste graphite-based lithium ion battery has been found in the prior art, which can effectively avoid waste of lithium resources.
Disclosure of Invention
The invention aims to provide a method for recovering lithium in a negative plate of a waste graphite lithium ion battery, and waste of lithium resources can be effectively avoided by recovering the waste graphite lithium ion battery by using the method.
In order to solve the problems, the following technical scheme is adopted: a method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery comprises the following steps:
step one, fully charging the waste graphite lithium ion battery;
step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell;
step three, the negative pole piece obtained in the step two is placed at the temperature of 150-550 ℃ for heat treatment;
step four, adding water into the negative plate subjected to heat treatment in the step three according to the solid-liquid ratio of 1:10-1:3, and stirring for 0.5-4h to obtain a solid-liquid mixture;
step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 20-80 meshes to obtain metal copper and an aqueous solution containing graphite powder;
and step six, adding sulfuric acid or hydrochloric acid into the aqueous solution containing the graphite powder obtained in the step five to adjust the pH value of the solution to 0.5-2.0, and then filtering to obtain the graphite powder and a solution containing a lithium compound, wherein the lithium compound is lithium sulfate or lithium chloride.
Wherein, the solid-to-liquid ratio in the fourth step is 1: 3.7.
Wherein the mass fraction of the sulfuric acid or the hydrochloric acid in the sixth step is 98%. When sulfuric acid is added, the main solute in the lithium compound-containing solution finally generated is lithium sulfate; when hydrochloric acid is added, the main solute in the lithium compound-containing solution finally produced is lithium chloride.
Preferably, after the solution containing the lithium compound is obtained in the sixth step, sodium hydroxide is added to adjust the pH of the solution to 10, then the solution is filtered, the filtrate obtained by filtering is fully reacted with sodium carbonate, and the lithium carbonate is obtained by evaporation and concentration.
Compared with the prior art, the invention has the following beneficial effects: the process of the invention is simple, firstly, the negative plate is heat treated, then water is added to obtain a solid-liquid mixture and is filtered, finally, hydrochloric acid or sulfuric acid is added to adjust the pH value of the solution to a lower range, and the solution containing the lithium compound (lithium sulfate or lithium chloride) can be obtained after filtering, and the solution containing the lithium compound can be used for producing various lithium compounds, such as lithium carbonate. The method can separate more than 17g of lithium from the negative pole piece of the 1kg waste graphite lithium ion battery, has high recovery rate, avoids the waste of lithium resources, protects the ecological environment and has extremely wide application prospect.
Detailed Description
The following examples are given to illustrate the present invention and it should be noted that the following examples are only for illustrative purposes and should not be construed as limiting the scope of the present invention, and that the modification and modification of the present invention by those of ordinary skill in the art are not essential to the present invention.
Example 1
A method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery comprises the following steps:
taking 1kg of rechargeable waste lithium ion battery with a positive electrode material of lithium cobaltate and a negative electrode material of graphite, and fully charging the battery by using a charging device;
step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell;
thirdly, the negative plate is placed at the temperature of 550 ℃ for heat treatment for 30 min;
step four, placing 270g of the heat-treated negative electrode sheet into a container, adding 1000mL of water, and stirring for 1 hour to obtain a solid-liquid mixture;
step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 80 meshes to obtain metal copper and an aqueous solution containing graphite powder;
and step six, adding 98% sulfuric acid into the aqueous solution containing the graphite powder obtained in the step five, continuously stirring, adjusting the pH value of the solution to 1.0, and then filtering to obtain the graphite powder and 930mL of lithium sulfate solution.
The concentration of lithium in the obtained lithium sulfate solution was measured by flame atomic absorption spectrometry, and the measurement result was 18.8g/L, that is, 17.5g of lithium was finally recovered.
Example 2
A method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery comprises the following steps:
taking 1kg of rechargeable waste lithium ion battery with a positive electrode material of lithium manganate and a negative electrode material of graphite, and fully charging the battery by using a charging device;
step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell;
thirdly, the negative plate is placed at the temperature of 200 ℃ for heat treatment for 2 hours;
step four, placing 270g of the heat-treated negative electrode sheet into a container, adding 870mL of water, and stirring for 1 hour to obtain a solid-liquid mixture;
step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 80 meshes to obtain metal copper and an aqueous solution containing graphite powder;
and step six, adding 98% hydrochloric acid into the aqueous solution containing the graphite powder obtained in the step five, continuously stirring, adjusting the pH value of the solution to 0.5, and then filtering to obtain the graphite powder and 830mL of lithium chloride solution.
The concentration of lithium in the obtained lithium chloride solution was measured by flame atomic absorption spectrometry, and the measurement result was 20.7g/L, that is, 17.2g of lithium was finally recovered.
Example 3
A method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery comprises the following steps:
taking 1kg of rechargeable waste lithium ion battery with a positive electrode material of lithium manganate and a negative electrode material of graphite, and fully charging the battery by using a charging device;
step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell;
thirdly, the negative plate is placed at the temperature of 300 ℃ for heat treatment for 1.5 h;
step four, placing 270g of the thermally treated negative electrode sheet into a container, adding 2700mL of water, and stirring for 1 hour to obtain a solid-liquid mixture;
step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 80 meshes to obtain metal copper and an aqueous solution containing graphite powder;
and step six, adding 98% hydrochloric acid into the aqueous solution containing the graphite powder obtained in the step five, continuously stirring, adjusting the pH value of the solution to 2.0, and then filtering to obtain the graphite powder and 2600mL of lithium chloride solution.
The concentration of lithium in the obtained lithium chloride solution was measured by flame atomic absorption spectrometry, and the measurement result was 6.62g/L, i.e., 17.2g of lithium was finally recovered.
Claims (3)
1. A method for recycling lithium in a negative electrode plate of a waste graphite lithium ion battery is characterized by comprising the following steps:
step one, fully charging the waste graphite lithium ion battery;
step two, disassembling the fully charged battery obtained in the step one to obtain a negative plate, a positive plate, a diaphragm and a battery shell;
step three, the negative pole piece obtained in the step two is placed at the temperature of 150-550 ℃ for heat treatment;
step four, adding water into the negative plate subjected to heat treatment in the step three according to the solid-to-liquid ratio of 1:3.7, and stirring for 0.5-4h to obtain a solid-liquid mixture;
step five, filtering the solid-liquid mixture obtained in the step four by using a vibrating screen of 20-80 meshes to obtain metal copper and an aqueous solution containing graphite powder;
and step six, adding sulfuric acid or hydrochloric acid into the aqueous solution containing the graphite powder obtained in the step five to adjust the pH value of the solution to 0.5-2.0, and then filtering to obtain the graphite powder and a solution containing a lithium compound, wherein the lithium compound is lithium sulfate or lithium chloride.
2. The method for recycling lithium in the negative electrode plates of the waste graphite-based lithium ion batteries according to claim 1, wherein the mass fraction of the sulfuric acid in the sixth step is 98%.
3. The method for recycling lithium in the negative electrode plates of the waste graphite-based lithium ion batteries according to claim 1, wherein after the solution containing the lithium compounds is obtained in the sixth step, sodium hydroxide is added to adjust the pH value of the solution to 10, then the solution is filtered, and the filtrate obtained by filtering is fully reacted with sodium carbonate and evaporated and concentrated to obtain lithium carbonate.
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| CN110668473A (en) * | 2019-08-13 | 2020-01-10 | 中国科学院过程工程研究所 | Method for recovering lithium from waste lithium ion battery negative electrode material |
| CN111268703A (en) * | 2019-10-10 | 2020-06-12 | 中国科学院生态环境研究中心 | Method for recovering lithium carbonate from waste lithium iron phosphate batteries |
| CN112259821A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering valuable metals from waste lithium ion batteries |
| CN114447465A (en) * | 2022-01-14 | 2022-05-06 | 清华大学深圳国际研究生院 | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154757A (en) * | 2006-09-29 | 2008-04-02 | 比亚迪股份有限公司 | Process for recovering carbon materials of battery cathode |
| CN102709621A (en) * | 2012-05-24 | 2012-10-03 | 上海应用技术学院 | Method for recycling high purity carbon material from waste lithium ion battery |
| CN103346365A (en) * | 2013-07-22 | 2013-10-09 | 田东 | Method for recycling negative material from waste lithium ion battery |
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| CN102390863B (en) * | 2011-08-15 | 2014-07-16 | 广东邦普循环科技有限公司 | Method for regenerating lithium titanate serving as anode material of waste lithium ion battery |
| CN107275701A (en) * | 2016-04-08 | 2017-10-20 | 深圳市沃特玛电池有限公司 | A kind of method that lithium carbonate is reclaimed from lithium ion battery |
| CN107394298A (en) * | 2017-06-21 | 2017-11-24 | 清华大学深圳研究生院 | Lithium resource recovery method on waste and old lithium ion battery negative plate |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101154757A (en) * | 2006-09-29 | 2008-04-02 | 比亚迪股份有限公司 | Process for recovering carbon materials of battery cathode |
| CN102709621A (en) * | 2012-05-24 | 2012-10-03 | 上海应用技术学院 | Method for recycling high purity carbon material from waste lithium ion battery |
| CN103346365A (en) * | 2013-07-22 | 2013-10-09 | 田东 | Method for recycling negative material from waste lithium ion battery |
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Address after: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee after: Hunan Jinkai Recycling Technology Co.,Ltd. Address before: No. 421, Dongjiang Circular Industrial Park, Dongyang City, Hunan Province Patentee before: HUNAN KEYKING CYCLE TECHNOLOGY Co.,Ltd. |